US4605596A - Additive for coating compositions - Google Patents

Additive for coating compositions Download PDF

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US4605596A
US4605596A US06562512 US56251283A US4605596A US 4605596 A US4605596 A US 4605596A US 06562512 US06562512 US 06562512 US 56251283 A US56251283 A US 56251283A US 4605596 A US4605596 A US 4605596A
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weight
additive
parts
acrylic
paint
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US06562512
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Grant C. Fry
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E I du Pont de Nemours and Co
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E I du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/7806Nitrogen containing -N-C=0 groups
    • C08G18/7818Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08Cellulose derivatives
    • C09D101/16Esters of inorganic acids
    • C09D101/18Cellulose nitrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31551Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31554Next to second layer of polyamidoester

Abstract

An additive for coating compositions which is a blend of
(A) 20-50% by weight of a polyisocyanate of one of the following formulas: ##STR1## where R1 is (CH2)6, (B) 1-15% by weight of an ester of a polyalkylene glycol alkyl alkylate, an alkyl phthalate or an alkyl aromatic phthalate
(C) 1-10% by weight of a blend of ultraviolet light stabilizers and
(D) 25-78% by weight of organic solvent; the additive can be added to acrylic lacquers, nitrocellulose lacquers, acrylic-alkyd enamels and acrylic polyurethane enamels to provide flexible finishes for flexible substrates used in automobile and truck bodies.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 451,249, filed Dec. 20, 1982, now U.S. Pat. No. 4,451,600.

BACKGROUND OF THE INVENTION

This invention relates to an additive for coating compositions which imparts flexibility to finishes formed from coating composition containing the additive.

For painting and refinishing of automobiles and trucks, the following paints are sold: acrylic lacquers as described in Meyer U.S. Pat. No. 4,168,249 issued Sept. 18, 1979, nitrocellulose lacquers, acrylic alkyd enamels as described in Miller U.S. Pat. No. 3,844,993 issued Oct. 29, 1974 and acrylic polyurethane enamels as described in Vasta U.S. Pat. No. 3,558,564 issued Jan. 26, 1971. These lacquers and enamels have a low level of flexibility and are primarily designed for application over rigid metal parts of automobiles and trucks. However, there are a number of parts of automobile and truck bodies that use flexible materials such as the flexible material covering the area between the bumper and the body of an automobile. When the aforementioned enamels or lacquers are applied over this flexible material and the material is flexed, the enamel or lacquer cracks, chips and peels off. A universal additive is needed that would form flexible finishes of these enamels and lacquers but would not degrade other important properties such as adhesion, weatherability, gasoline resistance, gloss and distinctness of image.

SUMMARY OF THE INVENTION

An additive for coating compositions which is a mixture of about

(A) 20-50% by weight of one of the following polyisocyanates: ##STR2## where R1 is (CH2)6 (B) 1-15% by weight of an ester selected from the group of a polyalkylene glycol alkyl alkylate, an alkyl phthalate or an alkyl aromatic phthalate,

(C) 1-10% by weight of a blend of ultraviolet light stabilizers and

(D) 25-78% by weight of an organic solvent.

DESCRIPTION OF THE INVENTION

The additive of this invention can be blended with the following coating compositions: acrylic lacquers, nitrocellulose lacquers, acrylic alkyd enamels and acrylic polyurethane enamels and provides finishes with excellent flexibility. The additive does not degrade other properties of these finishes such as gloss, adhesion, weatherability and gasoline resistance. Typically useful lacquer and enamel coating compositions are described in the aforementioned patents to Meyer, Miller and Vasta and the disclosure of these patents is hereby incorporated by reference.

Usually about 10-100% by weight, based on the weight of the coating composition, of the additive is blended with the coating composition. Preferably, about 20 to 70% by weight of the additive is used. Generally, about 2 parts by weight of acrylic or nitrocellulose lacquer are used per 1 part additive, 8 parts by weight acrylic alkyd enamel per 1 part of additive are used and 4 parts by weight of acrylic polyurethane enamel per 1 part additive are used.

The addition of the additive decreases the "pot" life of the coating composition. Generally, the aforementioned lacquers containing the additive must be used within about 4 hours after addition of the additive before the lacquer increases in viscosity or gels. The above enamels have a "pot" life of about 8 hours after addition of the additive.

The additive contains about 20-50% by weight, based on the weight of the additive, of a polyisocyanate. One useful polyisocyanate has the formula ##STR3## where R1 is (CH2)6.

Another useful polyisocyanate has the following formula ##STR4## where R1 is (CH2)6. The above polyisocyanate is 1,3,5-tris(6-isocyanatohexyl)1,3,5-triazine 2,4,6(1H, 3H, 5H)trione. Commercially available polyisocyanate compositions contain the above polyisocyanate and small amounts of higher molecular weight moieties such as dimers, trimers and hexamers of the polyisocyanate. Preferably, about 25 to 40% by weight of the polyisocyanate is used.

The additive contains 1-15% by weight, based on the weight of the additive of a polyalkylene glycol alkyl acrylate, an alkyl phthalate or an alkyl aromatic phthalate. Preferably, about 4 to 10% by weight of the polyalkylene glycol alkyl acrylate is used. Typically, polyethylene glycol di(2-ethylhexoate) is used. A typical alkyl phthalate that can be used is dioctyl phthalate and a typical alkyl aromatic phthalate is butyl benzyl phthalate.

The additive contains about 1-10% by weight based on the weight of the additive, of ultraviolet light stabilizers. Preferably, 5 to 10% by weight of ultraviolet light stabilizers are used.

Typical ultraviolet light stabilizers that are useful in the additive are as follows:

Benzophenones such as hydroxydodecycl benzophenone, 2,4-dihydroxybenzophenone, hydroxybenzophenones containing sulfonic acid groups, 2,4-dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'-trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2',4-trihydroxy-4'-alkoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone;

Triazoles such as 2-phenyl-4-(2'-4'-dihydroxybenzoyl)triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylphenyl)naphthotriazole;

Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of dialkyl-4-hydroxyphenyltriazines, hydroxyphenyl-1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,3,5-triazines, orthohydroxyaryl-s-triazine;

Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl phenyl benzoate, octyl phenyl benzoate, resorcinol dibenzoate.

Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-bis(2'-hydroxybenzoyl)benzene, metal derivatives of 3,5-di-t-butyl-4-hydroxyphenylpropionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri-pentaerythritol, phenyl- and naphthlene-substituted oxalic acid diamides, methyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, α,α'-bis(2-hydroxyphenyl)diisopropylbenzene, 3,5'-dibromo-2'-hydroxyacetophenone, ester derivatives of 4,4-bis(4'-hydroxyphenyl)pentanoic acid wherein there is at least one unsubstituted position ortho to the aromatic hydroxyl groups, organophosphorus sulfides such as bis(diphenylphosphinothioyl)monosulfide and bis(diphenylphosphinothioyl)disulfide, 4-benzoyl-6-(dialkylhydroxybenzyl)resorcinol, bis(3-hydroxy-4-benzoylphenoxy)diphenylsilane, bis(3-hydroxy-4-benzoylphenoxy)dialkylsilane, 1,8-naphthalimides, α-cyano-β,β-diphenylacrylic acid derivatives, bis(2-benzoxazolyl)alkanes, bis(2-napthoxazolyl)alkanes, methylene malonitriles containing aryl and heterocyclic substitutes, alkylenebis(dithio)carbamate, 4-benzoyl-3-hydroxyphenoxyethyl acrylate, 4-benzoyl-3-hydroxyphenoxyethyl methacrylate, aryl- or alkyl-substituted acrylonitriles, 3-methyl-5-isopropylphenyl-6-hydroxycoumarone.

Particularly useful ultraviolet light stabilizers that can be used are hindered amines of piperidyl derivatives such as those disclosed in Murayama et al., U.S. Pat. No. 4,061,616, issued Dec. 6, 1977, column 2, line 65, through column 4, line 2, and nickel compounds such as [1-phenyl-3-methyl-4-decanoylpyrazolate(5)]-Ni, bis[phenyldithiocarbamato]-Ni(II), and others listed in the above patent, column 8, line 44 through line 55.

The following blend of ultraviolet light stabilizers is particularly preferred 2-[2'-hydroxy-3',5'-1(1-1-dimethyl-propyl)phenyl]benzotriazole and di-[4-(2,2,6,6,-tetramethylpiperidyl)]sebecate. The stabilizers can be used in any ratio however, a 2:1 ratio of benzotriazole to sebacate is preferred.

The additive contains about 25-78% by weight, based on the weight of the additive of organic solvents. Preferably, about 40 to 66% by weight of organic solvents are used. Typically useful solvents are toluene, xylene, ethyl acetate and other organic solvents that do not contain hydroxyl groups or carboxyl groups.

After the additive is blended with a coating composition, the resulting blend is applied by conventional technique such as spraying, electrostatic spraying, brushing, dipping and the like to a substrate and dried at ambient temperatures. Typical flexible substrates to which these compositions can be applied are flexible thermoplastic polyurethane and injection molded polyurethanes. Low baking temperatures of 50°-125° C. can also be used to force dry the composition. The resulting finishes have good flexibility and retain the other good properties of the composition to which they were added.

The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated.

EXAMPLE 1

The following constituents were blended together to form the additive of this invention:

______________________________________             Parts By             Weight______________________________________Ethyl acetate       70.51Diethylene glycol monobutyl               7.90etherToluene             74.03Polyethylene glycol di               10.52 -(2-ethylhexoate)2-[2'-hydroxy-3',5'-1(1-1-               7.88dimethyl-propyl)phenyl]benzotriazoleDi-[4-(2,2,6,6,-tetramethyl-               3.95piperidyl)]sebacateDesmodur ® L2291-trimer of               92.18hexamethylene diisocyanateof the formulaTotal               266.97 ##STR5##______________________________________

where R1 is (CH2)6

A white acrylic lacquer was prepared by blending together the following ingredients:

______________________________________                Parts By                Weight______________________________________Mixed methyl esters of 16.71succinic, glutaric and adipic acidsIsopropanol            22.34Xylene                 31.97Alkyd Resin Solution (85%                  36.60solids in toluene of analkyd resin of coconut oil/ethylene glycol/phthalicanhydride having a GardnerHoldt Viscosity of Y-Z,measured at 25° C. and an acidnumber of about 7-10)Silicone Solution (1% solids in                  0.17Xylene of Silicone SF69)Polymethyl methacrylate Solution                  37.38(40% solids in a mixture oftoluene/acetone of polymethylmethacrylate having a relativeviscosity of 1.19 measured ona 0.5% polymer solids solutionusing dichloroethylene solventat 25° C.)Methyl methacrylate/diethyl                  67.40amino ethyl methacrylatecopolymer solution (40% solidsin a mixture of toluene/acetoneof a copolymer of 99% methylmethacrylate and 1% diethylamino ethyl methacrylate having arelative viscosity of 1.2 measuredas above.)Methyl methacrylate/butyl                  109.90acrylate copolymer solution(40% solids in a mixture oftoluene/acetone of a copolymerof 82% methylmethacrylate 18%butylacrylate having a relativeviscosity of 1.19 measured asabove.)Iminated Polymer Solution                  11.36(39% solids in toluene/isopropanolof a polymer of methyl methacrylate/ethyl acrylate/methacrylic acid/post reacted with propyleneiminein a weight ratio of 81/14.6/4.4/2.9 and the polymer has a relativeviscosity measured as above of1.2)Cellulose Acetate Butyrate                  41.83(CAB) solution (20% CABhaving a 37% butyrylcontent and a viscosityof 20 seconds in a solventof acetone and ethanol)CAB Solution (20% CAB having                  70.58a butyryl content of 37%and a viscosity of 2 secondsin a solvent of acetone andethanol)White Mill Base (55% titanium                  109.12dioxide pigment, 8% acrylicresin and 37% solvent oftoluene and "Cellosolve"acetateYellow Mill Base (22% yellow                  1.11iron oxide pigment, 19%acrylic resin and 59% tolueneTotal                  556.02______________________________________

About 67 parts of the above white acrylic lacquer and 33 parts of the above additive were blended together to form paint 1 and the resulting paint was sprayed onto a panel of a thermoplastic polyurethane flexible substrate and dried tack free at ambient temperature in 15 minutes. The gloss, distinctness of image, flexibility at room temperature and at -28° C. and gasoline resistance was measured and the panel was then exposed to outdoor weathering in Florida for 6 months and the gloss at 60° was measured and % gloss retention was determined. The results of these tests were recorded in the Table.

The following paints were formulated using commercial products which are used to improve flexibility of finishes.

______________________________________Paint A1 Part Du Pont Additive (22% solids  of 12 parts polymer of methyl  methacrylate/3-(2-methacryloxy ethyl)-  2,2-spiro cyclohexyl oxazolidene  95/5 ratio, 48 parts of polymer of  methyl methacrylate/butyl acrylate  85/15 ratio, 40 parts butyl benzyl  phthalate in a solvent of acetone and isopropanol)1 Part White acrylic lacquer (prepared above)Paint B1 Part Morton's Impact Coating  (31% solids of 72 parts polymer  of methyl methacrylate/butyl acrylate/  butyl methacrylate/hydroxy propyl  methacrylate 66/11/17/4 ratio,  18 parts polyester of butylene glycol/  ethylene glycol and lauric/myristic/  palmitic/stearic/oleic/adipic/o-phthalic  acids, ratio of acids to glycol is  3/1 and the polyester has a weight  average molecular weight of 13,000  and 10 parts dioctyl phthalate in a  solvent of toluene and "Cellosolve")1 Part White acrylic lacquer (prepared above)Paint C1 Part Inmont's Additive (19% solids of  polyester of dipropylene glycol  adipate chain extended with 1,6-  hexamethylene diisocyanate and  having a weight average molecular  weight of 23,000 in a solvent of ethyl  acetate and "Cellosolve")1 Part White acrylc lacquer (prepared above)Paint D1 Part Ditzler's Additive (50% solids of  a resin of polycaprolactone, poly-  propylene glycol and 3,-isocyanato-  methyl-3,3,5-trimethyl cyclohexyl  isocyanate in a molar ratio of  about 50/50/2, the resin is isocyanate  terminated and has a weight average  molecular weight of 23,000 in a solvent  of methyl ethyl ketone and toluene)4 Parts  White acrylic lacquer (prepared above)______________________________________

Each of the above paints A-D were each applied to a separate flexible substrate described above as the paint made with the additive of this invention and dried tack free at ambient temperature and gloss, distinctness of image, flexibility at room temperature at -28° C. and gasoline resistance for each was measured and 60° gloss retention was determined after 6 months outdoor weather in Florida. The results are shown in the Table.

The gloss and distinctness of image (DOI) of all the paints was above equivalent. The flexibility of Paint 1 containing the additive of the invention was better than Paint A and about equivalent to the other paints and the flexibility of Paint 1 at -28° C. was equal to Paint D and better than the other paints. The gasoline resistance of Paint 1 was better than the other paints. The outstanding feature is that Paint 1 has substantially better gloss retention after exposed to outdoor weathering in Florida for 6 months in comparison to the Paints A-D.

                                  TABLE__________________________________________________________________________            Gloss                  Gasoline                                         60° Gloss RetentionAdditive  DRY TIME            20°              60°                DOI*                    Flex Room Temp.                              -28° C.                                   Resistance                                         6 mos. Florida__________________________________________________________________________Paint 1   15 min.            52              84                50  9         8    5     71%Invention AdditivePaint A   15 min.            58              83                50  7         7    4     48%Du Pont AdditivePaint B   15 min.            56              81                50  10        5    4     34%MortonPaint C   15 min.            53              81                50  10        6    3     33%Inmont's AdditivePaint D   15 min.            52              80                50  9         8    4     27%Ditzler's Additive__________________________________________________________________________ *DOI-Distinctness of Image Ratings Flexibility  10  excellent no cracks, 7 acceptable, below 7 unacceptable Gasoline Resistance  5  excellent, 3 acceptable  some paint peeling off, below 3 unacceptable
EXAMPLE 2

A black nitrocellulose lacquer was prepared by blending together the following constituents:

______________________________________                  Parts By                  Weight______________________________________Isopropanol              22.19Xylene                   10.71Toluene                  68.11Aromatic petroleum naphtha                    7.43Blown castor oil         0.82Copper naphthenate       0.97Alkyd resin solution (described in Example 1)                    10.15Carbon black mill base (11% carbon black,                    47.5630% acrylic resin 60% solventof toluene/isopropanol)Nitrocellulose (1/2 second viscosity                    80.82dehydrated with isopropanol)Nitrocellulose (5-6 second viscosity                    13.48dehydrated with isopropanol)Ethylene glycol monoethyl ether acetate                    23.06Butyl acetate            33.01Methy isobutyl ketone    7.53Acetone                  117.06Butyl benzyl phthalate   23.73Trixylene phosphate      2.87Copolymer solution       39.72(43% solidscopolymer of methyl methacrylate/butylacrylate in solvents of acetone/toluene)Silicone solution (20% silicone resin in xylene)                    3.28Total                    512.50______________________________________

About 264.5 parts of the additive of this invention, prepared in Example 1, were blended with the above black lacquer and the resulting composition was sprayed onto a thermoplastic polyurethane flexible substrate and dried in 15 minutes to a tack free state at ambient temperatures. The gloss at 20° was 64, at 60° 91 and the distinctness of image was 40. The flexibility at room temperature was 9 and at -28° C. was 8. Gasoline resistance was 4. 60° gloss retention after 6 months weathering in Florida was 90%. The same tests and ratings were used in Example 1.

EXAMPLE 3

A white alkyd-acrylic resin paint was formulated by blending the following constituents:

______________________________________             Parts By             Weight______________________________________Alkyd resin solution               199.51(55% solids of a coco-nut oil/dehydrated castor oilfatty acids-pentaerythritol/benzoic acid-pentaerythritol/phthalic anhydride/with excesspentaerythritol in a weight ratioof 4.6/41.2/10.0/38.9/6.5)White mill base (58% titanium               176.03dioxide pigment, 15% acrylicresin, 27% aromatic solvent)Yellow mill base (40% ferric               0.63yellow pigment, 22% acrylicresin, 38% xylene)Black mill base (12% carbon               0.21black pigment, 31% acrylicresin, 56% xylene)Acrylic vinyl oxazoline               165.52polymer solution (59%polymer solid of polymer ofmethyl methacrylate, butylmethacrylate, hydroxy ethylmethacrylate, diethylamino ethyl methacrylateand vinyl oxazoline esterof linseed oil fatty acidsin weight ratio of 40/33/7/5/15 in toluene)Cobalt Drier Solution               5.82Xylene              69.59VM&P naphtha        43.52Turpentine          6.66Aromatic hydrocarbon               33.29Total               700.70______________________________________

About 160 parts of the additive of this invention, prepared in Example 1, were blended with the above with alkyd acrylic resin paint and the resulting composition was sprayed onto a thermoplastic polyurethane flexible substrate and dried in 30 minutes to a tack free state at ambient temperatures. The gloss at 20° was 80, at 60° 90, flexibility at room temperature was 10 and at -28° C. was 8. Gasoline resistance was 4. 60° Gloss retention after 6 months weathering in Florida was 84%. The same tests and ratings were used as in Example 1.

EXAMPLE 4

The following constituents were blended together to form an additive:

______________________________________                 Parts by Weight______________________________________Ethyl acetate           66.30Diethylene glycol monobutyl ether                   7.43Toluene                 69.62Polyethylene glycol di  9.90(2-ethylhexoate)2-[2'-hydroxy-3',5'-(1-1-dimethyl-                   7.41propyl) phenyl] benzotriazoleDi-[4-(2,2,6,6,-tetramethyl-piperidyl)]                   3.71sebacate"Desmodur" N3390-isocyanurate trimer of                   105.31formula                   269.68 ##STR6##______________________________________

where R1 is (CH2)6

About 67 parts of the white acrylic lacquer prepared in Example 1 and 33 parts of the above additive were blended together to form a paint and the resulting paint was sprayed onto a panel of thermoplastic polyurethane flexible substrate and dried tack free at ambient temperature in 15 minutes. Later, the gloss, distinctness of image, flexibility at room temperature and at -28° C. and gasoline resistance were measured. The results are very similar to paint 1 of Example 1 shown in the Table.

About 264.5 parts of the above additive were blended with 512 parts of the black lacquer of Example 2 and the resulting composition was sprayed onto a panel of thermoplastic polyurethane flexible substrate and dried in 15 minutes to a tack free state at ambient temperatures. The gloss at 20° and 60°, the distinctness of image and flexibility at room temperature and at -28° C. and gasoline resistance were measured. The results are very similar to those obtained in Example 2.

About 160 parts of the above additive were blended with the above 700 parts of the alkyd acrylic resin paint of Example 3 and the resulting composition was sprayed onto a panel of a thermoplastic polyurethane flexible substrate and dried in 30 minutes to a tack free state at ambient temperatures. The gloss at 20° and 60°, flexibility at room temperature and at -28° C. and gasoline resistance were measured. The results are very similar to those obtained in Example 3.

Claims (10)

I claim:
1. An additive for coating compositions which comprises about
(A) 20-50% by weight of a polyisocyanate of the formula ##STR7## where R' is (CH2)6 ; (B) 1-15% by weight of an ester of [polyethylene glycol diethylhexoate]polyethylene glycol di(2-ethylhexoate);
(C) 1-10% by weight of a blend of ultraviolet light stabilizers consisting essentially of 2-[2'-hydroxy-3',5'-1(1-1-dimethylpropyl)phenyl]benzotriazole and di-[4-(2,2,6,6-tetramethyl-piperidyl)]sebacate and
(D) 25-78% by weight of organic solvent comprising ethyl acetate, toluene and diethylene glycol monobutyl ether.
2. A coating composition containing 10-70% by weight of a binder and 90-30% by weight of a liquid carrier and containing about 10-100% by weight, based on the weight of the coating composition of the additive of claim 1.
3. The coating composition of claim 2 in which the composition contains pigments in a pigment to binder weight ratio of about 1:100 to 200:100.
4. The coating composition of claim 3 in which the binder comprises an acrylic polymer.
5. The coating composition of claim 3 in which the binder comprises a nitrocellulose polymer.
6. The coating composition of claim 3 in which the binder comprises an acrylic vinyl oxazoline ester polymer.
7. The coating composition of claim 3 in which the binder comprises an acrylic resin containing reactive hydroxyl groups and a polyisocyanate crosslinking resin.
8. A flexible substrate coated with the composition of claim 2.
9. The flexible substrate of claim 8 in which the substrate is a thermoplastic polyurethane.
10. The flexible substrate of claim 8 which the substrate is an injection molded polyurethane.
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US4677028A (en) * 1985-02-20 1987-06-30 Akzo N.V. Thixotropic coating composition, process for coating a substrate with such coating composition and the coated substrate thus obtained
US4711918A (en) * 1985-08-16 1987-12-08 Bayer Aktiengesellschaft Use of polyisocyanates or polyisocyanate mixtures as additives for aqueous emulsion paints
US4983655A (en) * 1988-06-24 1991-01-08 Sunstar Giken Kabushiki Kaisha Blocked polyisocyanurate compound and plastisol composition containing same
US5110673A (en) * 1989-11-24 1992-05-05 Huels Aktiengesellschaft Fusible adhesives for textile fastening inserts
US5114789A (en) * 1987-11-03 1992-05-19 Eastman Kodak Company Protective and decorative sheet material having a transparent topcoat
US5554739A (en) * 1994-12-15 1996-09-10 Cabot Corporation Process for preparing carbon materials with diazonium salts and resultant carbon products
US5559169A (en) * 1994-12-15 1996-09-24 Cabot Corporation EPDM, HNBR and Butyl rubber compositions containing carbon black products
US5571311A (en) * 1994-12-15 1996-11-05 Cabot Corporation Ink jet ink formulations containing carbon black products
US5575845A (en) * 1994-12-15 1996-11-19 Cabot Corporation Carbon black products for coloring mineral binders
US5630868A (en) * 1994-12-15 1997-05-20 Cabot Corporation Ink jet ink formulations containing modified carbon products
US5653927A (en) * 1995-06-07 1997-08-05 Avery Dennison Corporation Control of metallic appearance in automotive cast paint films
US5672198A (en) * 1994-12-15 1997-09-30 Cabot Corporation Aqueous inks and coatings containing modified carbon products
US5698016A (en) * 1996-06-14 1997-12-16 Cabot Corporation Compositions of modified carbon products and amphiphilic ions and methods of using the same
US5707697A (en) * 1987-03-27 1998-01-13 Avery Dennison Corporation Dry paint transfer product having high DOI automotive paint coat
US5707432A (en) * 1996-06-14 1998-01-13 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5713988A (en) * 1994-12-15 1998-02-03 Cabot Corporation Non-aqueous inks and coatings containing modified carbon products
US5725712A (en) * 1987-03-27 1998-03-10 Avery Dennison Corporation Dry paint transfer process for making high DOI automotive body panels
US5747562A (en) * 1996-06-14 1998-05-05 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5807494A (en) * 1994-12-15 1998-09-15 Boes; Ralph Ulrich Gel compositions comprising silica and functionalized carbon products
US5851280A (en) * 1994-12-15 1998-12-22 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5863323A (en) * 1995-05-22 1999-01-26 Cabot Corporation Mineral binders colored with silicon-containing carbon black
US5916934A (en) * 1995-05-22 1999-06-29 Cabot Corporation Elastomeric compounds incorporating partially coated carbon blacks
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US6113838A (en) * 1995-06-07 2000-09-05 Avery Dennison Corporation Control of metallic appearance in automotive cast paint films
US6323273B1 (en) 1995-05-22 2001-11-27 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks
US6551432B1 (en) 1987-03-27 2003-04-22 Avery Dennison Corporation Dry paint transfer process and product
US6590012B2 (en) * 1997-04-28 2003-07-08 Seiko Epson Corporation Ink composition capable of realizing light fast image
US6863713B1 (en) 1996-06-14 2005-03-08 Cabot Corporation Method to adsorb an adsorbate using modified carbonaceous material
US6972303B1 (en) * 1998-06-24 2005-12-06 Seiko Epson Corporation Ink composition providing image excellent in light stability
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558564A (en) * 1969-03-27 1971-01-26 Du Pont Thermosetting coating composition of an organic polyisocyanate and a polymer having pendant hydroxyl containing ester groups
US3844993A (en) * 1971-06-28 1974-10-29 Du Pont Floor mop having pivotable handle for changing directions air-drying coating composition of an acrylic enamel and an isocyanate cross-linking agent
US4131571A (en) * 1975-12-29 1978-12-26 E. I. Du Pont De Nemours And Company Polyurethane metallic enamel
US4168249A (en) * 1977-07-01 1979-09-18 E. I. Du Pont De Nemours And Company Acrylic lacquer coating composition of polymethyl methacrylate, copolymers of methyl methacrylate, cellulose acetate butyrate and a polyester plasticizer
JPS55120644A (en) * 1979-02-13 1980-09-17 Showa Electric Wire & Cable Co Ltd Flame-retardant and heat-resistant ethylene-propylene copolymer composition
US4315848A (en) * 1979-05-10 1982-02-16 Ciba-Geigy Corporation 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions
US4389502A (en) * 1981-12-24 1983-06-21 E. I. Du Pont De Nemours And Company Clear air-dry acrylic lacquer coating composition
US4419513A (en) * 1980-09-09 1983-12-06 Bayer Aktiengesellschaft Isocyanato-isocyanurates, and process for the production thereof
US4442256A (en) * 1982-12-16 1984-04-10 E. I. Du Pont De Nemours And Company Additive for alkyd resin coating compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558564A (en) * 1969-03-27 1971-01-26 Du Pont Thermosetting coating composition of an organic polyisocyanate and a polymer having pendant hydroxyl containing ester groups
US3844993A (en) * 1971-06-28 1974-10-29 Du Pont Floor mop having pivotable handle for changing directions air-drying coating composition of an acrylic enamel and an isocyanate cross-linking agent
US4131571A (en) * 1975-12-29 1978-12-26 E. I. Du Pont De Nemours And Company Polyurethane metallic enamel
US4168249A (en) * 1977-07-01 1979-09-18 E. I. Du Pont De Nemours And Company Acrylic lacquer coating composition of polymethyl methacrylate, copolymers of methyl methacrylate, cellulose acetate butyrate and a polyester plasticizer
JPS55120644A (en) * 1979-02-13 1980-09-17 Showa Electric Wire & Cable Co Ltd Flame-retardant and heat-resistant ethylene-propylene copolymer composition
US4315848A (en) * 1979-05-10 1982-02-16 Ciba-Geigy Corporation 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions
US4419513A (en) * 1980-09-09 1983-12-06 Bayer Aktiengesellschaft Isocyanato-isocyanurates, and process for the production thereof
US4389502A (en) * 1981-12-24 1983-06-21 E. I. Du Pont De Nemours And Company Clear air-dry acrylic lacquer coating composition
US4442256A (en) * 1982-12-16 1984-04-10 E. I. Du Pont De Nemours And Company Additive for alkyd resin coating compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Hawley, The Condensed Chemical Dictionary, 1977, p. 497. *
Sumitomo Chemical Co., Chemical Abstracts, 99: 105287w. *

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US4677028A (en) * 1985-02-20 1987-06-30 Akzo N.V. Thixotropic coating composition, process for coating a substrate with such coating composition and the coated substrate thus obtained
US4711918A (en) * 1985-08-16 1987-12-08 Bayer Aktiengesellschaft Use of polyisocyanates or polyisocyanate mixtures as additives for aqueous emulsion paints
US6649003B1 (en) 1987-03-27 2003-11-18 Avery Dennison Corporation Dry paint transfer lamination process for making high DOI automotive body panels
US20040123941A1 (en) * 1987-03-27 2004-07-01 Spain Patrick L. Dry paint transfer-lamination process for making high doi automotive body panels
US6835267B1 (en) 1987-03-27 2004-12-28 Avery Dennison Corporation Dry paint transfer process and product
US5916643A (en) * 1987-03-27 1999-06-29 Avery Dennison Corporation Dry paint transfer-laminated body panels having deep-draw high DOI automotive paint coat
US5707697A (en) * 1987-03-27 1998-01-13 Avery Dennison Corporation Dry paint transfer product having high DOI automotive paint coat
US6838130B1 (en) 1987-03-27 2005-01-04 Avery Dennison Corporation Dry paint transfer process and product
US6966962B2 (en) 1987-03-27 2005-11-22 Avery Dennison Corporation Dry paint transfer-lamination process for making high DOI automotive body panels
US20040123942A1 (en) * 1987-03-27 2004-07-01 Spain Patrick L. Dry paint transfer process for making deep-draw high doi automotive body panels
US5725712A (en) * 1987-03-27 1998-03-10 Avery Dennison Corporation Dry paint transfer process for making high DOI automotive body panels
US6984280B2 (en) 1987-03-27 2006-01-10 Avery Dennison Coporation Dry paint transfer process for making deep-draw high doi automotive body panels
US6579397B1 (en) 1987-03-27 2003-06-17 Avery Dennison Corporation Dry paint transfer process for making deep draw high DOI automotive body panels
US6551432B1 (en) 1987-03-27 2003-04-22 Avery Dennison Corporation Dry paint transfer process and product
US5114789A (en) * 1987-11-03 1992-05-19 Eastman Kodak Company Protective and decorative sheet material having a transparent topcoat
US4983655A (en) * 1988-06-24 1991-01-08 Sunstar Giken Kabushiki Kaisha Blocked polyisocyanurate compound and plastisol composition containing same
US5110673A (en) * 1989-11-24 1992-05-05 Huels Aktiengesellschaft Fusible adhesives for textile fastening inserts
US6494946B1 (en) 1994-12-15 2002-12-17 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5575845A (en) * 1994-12-15 1996-11-19 Cabot Corporation Carbon black products for coloring mineral binders
US5571311A (en) * 1994-12-15 1996-11-05 Cabot Corporation Ink jet ink formulations containing carbon black products
US5807494A (en) * 1994-12-15 1998-09-15 Boes; Ralph Ulrich Gel compositions comprising silica and functionalized carbon products
US5851280A (en) * 1994-12-15 1998-12-22 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5630868A (en) * 1994-12-15 1997-05-20 Cabot Corporation Ink jet ink formulations containing modified carbon products
US5900029A (en) * 1994-12-15 1999-05-04 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5554739A (en) * 1994-12-15 1996-09-10 Cabot Corporation Process for preparing carbon materials with diazonium salts and resultant carbon products
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US5713988A (en) * 1994-12-15 1998-02-03 Cabot Corporation Non-aqueous inks and coatings containing modified carbon products
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US6740151B2 (en) 1994-12-15 2004-05-25 Cabot Corporation Reaction of carbon black with diazonium salts, resultant carbon black products and their uses
US5916934A (en) * 1995-05-22 1999-06-29 Cabot Corporation Elastomeric compounds incorporating partially coated carbon blacks
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US5863323A (en) * 1995-05-22 1999-01-26 Cabot Corporation Mineral binders colored with silicon-containing carbon black
US7199176B2 (en) 1995-05-22 2007-04-03 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks
US6323273B1 (en) 1995-05-22 2001-11-27 Cabot Corporation Elastomeric compounds incorporating silicon-treated carbon blacks
US5653927A (en) * 1995-06-07 1997-08-05 Avery Dennison Corporation Control of metallic appearance in automotive cast paint films
US6113838A (en) * 1995-06-07 2000-09-05 Avery Dennison Corporation Control of metallic appearance in automotive cast paint films
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US5749950A (en) * 1996-06-14 1998-05-12 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5747562A (en) * 1996-06-14 1998-05-05 Cabot Corporation Ink and coating compositions containing silicon-treated carbon black
US5707432A (en) * 1996-06-14 1998-01-13 Cabot Corporation Modified carbon products and inks and coatings containing modified carbon products
US5919855A (en) * 1997-02-11 1999-07-06 Cabot Corporation Use of modified carbon black in gas-phase polymerizations
US6590012B2 (en) * 1997-04-28 2003-07-08 Seiko Epson Corporation Ink composition capable of realizing light fast image
US6972303B1 (en) * 1998-06-24 2005-12-06 Seiko Epson Corporation Ink composition providing image excellent in light stability
US8828181B2 (en) 2010-04-30 2014-09-09 E I Du Pont De Nemours And Company Temperature switchable adhesives comprising a crystallizable oil
CN103834286B (en) * 2012-11-23 2016-12-07 展辰新材料集团股份有限公司 A polyurethane elastomeric coating cracks
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